Heinrich et al.
3
2
) 7.5 Hz, 2 H), 7.27 (d, J ) 7.8 Hz, 2 H); 13C NMR (C6D6, 90
Hz, 2 × CH), 129.2 (q, JCF ) 32.2 Hz, Cq), 130.0 (2 × CH),
2
MHz) δ ) 26.3 (CH2), 31.2 (CH2), 36.2 (CH2), 41.3 (CH), 43.7
(CH), 53.9 (CH), 84.7 (CH), 122.4 (2 × CH), 125.6 (CH), 128.1
(2 × CH), 128.8 (2 × CH), 129.0 (2 × CH), 129.8 (CH), 141.2
(Cq), 153.1 (Cq); MS (EI) m/z 276 (27) [M+], 171 (55), 105 (37),
91 (100), 77 (48); HRMS (EI) calcd for C19H20N2 [M+] 276.1627,
found 276.1623.
132.5 (q, JCF ) 32.3 Hz, Cq), 141.7 (Cq), 153.8 (Cq), 169.8 (Cq);
19F NMR (C6D6, 235 MHz) δ -62.2 (CF3), -62.5 (CF3); MS (EI)
m/z 418 (3) [M+], 399 (3), 339 (4) 328 (6), 305 (8), 245 (18), 201
(8), 185 (14), 173 (62), 159 (59), 145 (100); HRMS (EI) calcd for
C19H16F6N2O2 [M+] 418.1116, found 418.1117.
4-[2-(4-Methoxycarbonylphenylazo)-3-cyanopropyl]benzoic
Acid Methyl Ester (6h). Purification by column chromatography
(P/EtOAc ) 3:1) gave 6h as a yellow solid: Rf ) 0.25 (P/EtOAc
) 3:1); mp ) 74 °C; 1H NMR (C6D6, 360 MHz) δ 2.13 (dd, 3J )
5.0 Hz, J ) 16.6 Hz, 1 H), 2.19 (dd, J ) 5.9 Hz, J ) 16.6 Hz,
1 H), 2.84 (dd, 3J ) 6.8 Hz, 2J ) 14.0 Hz, 1 H), 2.99 (dd, 3J ) 7.2
Hz, 2J ) 14.0 Hz, 1 H), 3.54 (s, 3 H), 3.56 (s, 3 H), 3.93-4.02 (m,
1 H), 6.93 (d, J ) 8.2 Hz, 2 H), 7.61 (d, J ) 8.2 Hz, 2 H), 7.99
(d, 3J ) 8.2 Hz, 2 H), 8.06 (d, 3J ) 8.2 Hz, 2 H); 13C NMR (C6D6,
90 MHz) δ 20.1 (CH2), 38.4 (CH2), 51.5 (CH3), 51.8 (CH3), 73.0
(CH), 117.0 (Cq), 122.6 (2 × CH), 129.5 (Cq), 129.8 (2 × CH),
130.2 (2 × CH), 130.9 (2 × CH), 132.9 (Cq), 141.9 (Cq), 154.0
(Cq), 165.9 (Cq), 166.4 (Cq); MS (EI) m/z 365 (11) [M+], 334 (8),
242 (4), 211 (5), 188 (5), 163 (76), 151 (12), 149 (16), 136 (12),
135 (100), 120 (16), 103 (15); HRMS (EI) calcd for C20H19N3O4
[M+] 365.1375, found 365.1370.
4-[2-(4-Methoxycarbonylphenylazo)-5-oxohexyl]benzoic Acid
Methyl Ester (6i). Purification by column chromatography (P/
EtOAc ) 3:1) gave 6i as a yellow oil: Rf ) 0.30 (P/EtOAc )
3:1); 1H NMR (C6D6, 360 MHz) δ 1.60 (s, 3 H), 1.93-2.05 (m, 3
Acetic Acid 3-(4-Carboxy-3-chlorophenyl)-2-(4-carboxy-3-
chlorophenylazo)propyl Ester (6d). Purification by column chro-
matography (CHCl3/MeOH ) 7:3) gave 6d as a yellow foam: Rf
2
3
2
1
) 0.70 (CHCl3/MeOH ) 2:1); H NMR (CD3OD, 360 MHz) δ
1.97 (s, 3 H), 3.19 (dd, 3J ) 5.5 Hz, 2J ) 14.0 Hz, 1 H), 3.28 (dd,
3J ) 8.5 Hz, 2J ) 14.0 Hz, 1 H), 4.20-4.25 (m, 1 H), 4.49 (dd, 3J
) 3.5 Hz, 2J ) 11.5 Hz, 1 H) 4.59 (dd, 3J ) 8.0 Hz, 2J ) 11.5 Hz,
3
3
4
3
4
1 H), 7.11 (dd, J ) 1.8 Hz, J ) 7.9 Hz, 1 H), 7.24 (d, J ) 1.8
Hz, 1 H), 7.51 (d, J ) 7.9 Hz, 1 H), 7.55 (dd, J ) 1.8 Hz, J )
3
3
2
4
3
7.9 Hz, 1 H), 7.58 (d, J ) 1.8 Hz, 1 H), 7.63 (d, J ) 7.9 Hz, 1
H); 13CNMR (CD3OD, 90 MHz) δ 20.6 (CH3), 36.6 (CH2), 65.6
(CH2), 78.2 (CH), 122.3 (CH), 123.9 (CH), 128.9 (CH), 130.5 (CH),
130.7 (CH), 132.2 (CH), 132.4 (Cq), 132.5 (Cq), 136.7 (Cq), 141.6
(Cq), 142.3 (Cq), 153.2 (Cq), 171.9 (Cq), 172.4 (2 × Cq); MS (ESI)
m/z 437 [M+ - H, C19H1535Cl2N2O6], 439 [M+ - H, C19H1535Cl37-
ClN2O6]; HRMS (ESI) calcd for C19H1635Cl2N2O6 [M+] 437.0307,
found 437.0299.
4-[3-Acetoxy-2-(4-methoxycarbonylphenylazo)propyl]benzo-
ic Acid Methyl Ester (6e). Purification by column chromatography
(P/EtOAc ) 3:1) gave 6e as a yellow solid: Rf ) 0.60 (P/EtOAc
3
2
H), 2.11-2.20 (m, 1 H), 2.84 (dd, J ) 5.6 Hz, J ) 13.8 Hz, 1
H), 3.08 (dd, 3J ) 7.9 Hz, 2J ) 13.8 Hz, 1 H), 3.48 (s, 3 H), 3.49
(s, 3 H), 3.86-3.92 (m, 1 H), 6.97 (d, 3J ) 8.3 Hz, 2 H), 7.60 (d,
1
) 2:1); mp ) 88 °C; H NMR (C6D6, 360 MHz) δ 1.60 (s, 3 H),
2.83 (dd, 3J ) 6.3 Hz, 2J ) 13.9 Hz, 1 H), 3.00 (dd, 3J ) 7.9 Hz,
3J ) 9.0 Hz, 2 H), 7.98 (d, J ) 8.3 Hz, 2 H), 8.06 (d, J ) 9.0
Hz, 2 H); 13C NMR (C6D6, 90.6 MHz) δ 27.4 (CH2), 29.4 (CH3),
39.6 (CH2), 40.3 (CH2), 51.5 (CH3), 51.8 (CH3), 78.4 (CH), 122.4
(2 × CH), 129.0 (Cq), 129.9 (2 × CH), 130.0 (2 × CH), 130.9 (2
× CH), 132.4 (Cq), 143.9 (Cq), 154.5 (Cq), 166.0 (Cq), 166.5 (Cq),
205.6 (Cq); MS (EI) m/z 396 (2) [M+], 365 (10), 234 (11), 233
(71), 201 (68), 175 (12), 163 (34), 149 (20), 135 (100), 120 (25);
HRMS (EI) calcd for C22H24N2O5 [M+] 396.1685, found 396.1706;
HRMS (EI) calcd for C21H21N2O4 [M+ - CH3O] 365.1501, found
365.1498.
3
3
2J ) 13.9 Hz, 1 H), 3.48 (s, 3 H), 3.51 (s, 3 H), 4.20-4.28 (m, 1
3
2
3
H), 4.39 (dd, J ) 3.6 Hz, J ) 11.5 Hz, 1 H) 4.56 (dd, J ) 7.9
2
3
3
Hz, J ) 11.5 Hz, 1 H), 6.92 (d, J ) 8.3 Hz, 2 H), 7.63 (d, J )
3
3
8.6 Hz, 2 H), 8.01 (d, J ) 8.3 Hz, 2 H), 8.07 (d, J ) 8.6 Hz, 2
H); 13C NMR (C6D6, 90 MHz) δ 20.2 (CH3), 36.5 (CH2), 51.5
(CH3), 51.8 (CH3), 64.5 (CH2), 77.3 (CH), 122.5 (2 × CH), 129.3
(Cq), 129.8 (2 × CH), 130.1 (2 × CH), 130.9 (2 × CH), 132.6
(Cq), 142.7 (Cq), 154.5 (Cq), 165.9 (Cq), 166.4 (Cq), 169.8 (Cq);
MS (EI) m/z 398 (6) [M+], 367 (5), 279 (5), 235 (10), 163 (72),
136 (10), 135 (100), 102 (10); HRMS (EI) calcd for C21H22N2O6
[M+] 398.1478, found 398.1472.
4-[3-Acetoxy-2-methyl-2-(4-methoxycarbonylphenylazo)pro-
pyl]benzoic Acid Methyl Ester (6j). Purification by column
chromatography (P/EtOAc ) 4:1) gave 6j as a yellow oil: Rf )
0.60 (P/EtOAc ) 4:1); 1H NMR (C6D6, 250 MHz) δ 1.14 (s, 3 H),
1.64 (s, 3 H), 2.94 (d, J ) 13.3 Hz, 1 H), 3.06 (d, J ) 13.3 Hz,
1 H), 3.49 (s, 3 H), 3.50 (s, 3 H), 4.41 (s, 2 H), 6.95 (d, J ) 8.3
Hz, 2 H), 7.61 (d, J ) 8.8 Hz, 2 H), 7.97 (d, J ) 8.3 Hz, 2 H),
8.09 (d, 3J ) 8.8 Hz, 2 H); 13C NMR (C6D6, 63 MHz) δ 19.6 (CH3),
20.3 (CH3), 42.1 (CH2), 51.6 (CH3), 51.8 (CH3), 67.9 (CH2), 73.3
(Cq), 122.4 (2 × CH), 129.3 (Cq), 129.7 (2 × CH), 130.9 (2 ×
CH), 131.0 (2 × CH), 132.4 (Cq), 142.1 (Cq), 154.4 (Cq), 165.9
(Cq), 166.5 (Cq), 169.8 (Cq); MS (EI) m/z 382 (2) [M+ - CH2O],
381 (8) [M+ - CH3O], 249 (34), 217 (23), 207 (34), 189 (26), 175
(25), 163 (53), 149 (34), 135 (100); HRMS (EI) calcd for
C22H24N2O6 [M+] 412.1634, found 412.1626; HRMS (EI) calcd
for C21H21N2O5 [M+ - CH3O] 381.1450, found 381.1445.
2-[3-Acetoxy-2-(2-methoxycarbonylphenylazo)propyl]benzo-
ic Acid Methyl Ester (6f). Purification by column chromatography
(P/EtOAc ) 3:1) gave 6f as a yellow oil: Rf ) 0.25 (P/EtOAc )
2
2
1
4:1); H NMR (C6D6, 360 MHz) δ 1.69 (s, 3 H), 3.46 (s, 3 H),
3
3.48 (s, 3 H), 3.60 (dd, 3J ) 7.9 Hz, 2J ) 13.5 Hz, 1 H), 3.71 (dd,
3
3
3J ) 5.8 Hz, 2J ) 13.5 Hz, 1 H), 4.56 (dd, 3J ) 3.8 Hz, 2J ) 11.1
3
2
Hz, 1 H) 4.58-4.65 (m, 1 H), 4.78 (dd, J ) 7.6 Hz, J ) 11.1
Hz, 1 H), 6.87-6.93 (m, 2 H), 6.95-7.04 (m, 3 H), 7.23 (dd, 4J )
3
4
3
1.1 Hz, J ) 7.9 Hz, 1 H), 7.61 (dd, J ) 1.3 Hz, J ) 7.7 Hz, 1
H), 7.88 (d, J ) 7.9 Hz, 1 H); 13C NMR (C6D6, 90 MHz) δ 20.4
3
(CH3), 35.0 (CH2), 51.5 (CH3), 51.8 (CH3), 64.8 (CH2), 77.6 (CH),
119.2 (CH), 126.8 (CH), 128.8 (Cq), 129.3 (CH), 129.8 (CH), 130.4
(Cq), 131.4 (CH), 131.8 (CH), 132.0 (CH), 132.7 (CH), 140.1 (Cq),
152.1 (Cq), 167.2 (Cq), 167.5 (Cq), 170.0 (Cq); MS (EI) m/z 398
(8) [M+], 279 (6), 235 (22), 163 (65), 135 (100), 115 (8), 91 (12);
HRMS (EI) calcd for C21H22N2O6 [M+] 398.1478, found 398.1472.
4-[3-Hydroxy-2-methyl-2-(4-methoxycarbonylphenylazo)pro-
pyl]benzoic Acid Methyl Ester (6k). Purification by column
chromatography (P/EtOAc ) 2:1) gave 6k as a yellow oil: Rf )
0.50 (P/EtOAc ) 2:1); 1H NMR (C6D6, 360 MHz) δ 1.10 (s, 3 H),
Acetic Acid 3-(4-Trifluoromethyl-phenyl)-2-(4-trifluorometh-
ylphenylazo)propyl Ester (6g). Purification by column chroma-
tography (P/EtOAc ) 10:1) gave 6g as a yellow solid: Rf ) 0.25
2
2
2.97 (d, J ) 13.0 Hz, 1 H), 3.07 (d, J ) 13.0 Hz, 1 H), 3.48 (s,
1
3 H), 3.49 (s, 3 H), 3.62 (d, 2J ) 11.5 Hz, 1 H), 3.69 (d, 2J ) 11.5
(P/EtOAc ) 10:1); mp ) 79 °C; H NMR (C6D6, 360 MHz) δ
1.63 (s, 3 H), 2.78 (dd, 3J ) 2.5 Hz, 2J ) 13.7 Hz, 1 H), 2.95 (dd,
3J ) 7.9 Hz, 2J ) 13.7 Hz, 1 H), 4.14-4.23 (m, 1 H), 4.33 (dd, 3J
) 4.0 Hz, 2J ) 11.5 Hz, 1 H) 4.49 (dd, 3J ) 7.9 Hz,2J ) 11.5 Hz,
3
3
Hz, 1 H), 7.10 (d, J ) 8.3 Hz, 2 H), 7.54 (d, J ) 8.6 Hz, 2 H),
8.03 (d, J ) 8.3 Hz, 2 H), 8.10 (d, J ) 8.6 Hz, 2 H); 13C NMR
(C6D6, 90 MHz) δ 19.6 (CH3), 41.5 (CH2), 51.6 (CH3), 51.8 (CH3),
66.9 (CH2), 75.2 (Cq), 122.4 (2 × CH), 129.2 (Cq), 129.7 (2 ×
CH), 130.9 (2 × CH), 131.2 (2 × CH), 132.4 (Cq), 142.9 (Cq),
3
3
1 H), 6.82 (d, 3J ) 7.9 Hz, 2 H), 7.27 (d, J ) 7.9 Hz, 2 H), 7.31
3
(d, 3J ) 7.9 Hz, 2 H), 7.48 (d, 3J ) 7.9 Hz, 2 H); 13CNMR (C6D6,
90 MHz) δ 20.0 (CH3), 36.1 (CH2), 64.2 (CH2), 77.0 (CH), 122.8
154.4 (Cq), 166.0 (Cq), 166.7 (Cq); MS (EI) m/z 340 (34) [M+
-
1
1
(2×CH), 124.4 (q, JCF ) 273.0 Hz, Cq), 124.9 (q, JCF ) 272.1
CH2O], 309 (13), 207 (36), 175 (28), 163 (25), 151 (34), 150 (23),
149 (100), 136 (15), 135 (58), 122 (15), 121 (28), 120 (18); HRMS
3
3
Hz, Cq) 125.6 (q, JCF ) 3.8 Hz, 2 × CH), 126.5 (q, JCF ) 3.9
482 J. Org. Chem., Vol. 72, No. 2, 2007